Golf ball composition and golf ball

ABSTRACT

A golf ball having a good rebound and excellent flight performance can be obtained using a golf ball composition which contains a diene polymer having an aluminum catalyst residue content of not more than 650 ppm.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a)on Patent Application No. 2011-269007 filed in Japan on Dec. 8, 2011,the entire contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a golf ball composition from which golfballs having an especially good rebound and an outstanding flightperformance can be obtained. The invention also relates to a golf ballformed using such a composition.

2. Prior Art

In order to confer golf balls with an excellent rebound, variousimprovements have hitherto been carried out, not only on the ballconstruction, but also on the materials from which the ball is formed.

For example, in order to develop a polymeric material having highthermal properties (e.g., thermal stability) and mechanical properties(e.g., tensile modulus, flexural modulus), JP-A 2000-313710 discloses acatalyst composition which is capable of producing a conjugated dienepolymer having a high cis-1,4 structure content in the microstructureand having a narrow molecular weight distribution. JP-A 2002-282393 andJP-A 2002-338737 describe solid golf balls having a good flightperformance, in which balls a solid core has been formed using apolybutadiene rubber obtained with, for example, the catalystcomposition described in JP-A 2000-313710.

International Application No. 2006/049016 describes art which, by usingan yttrium compound as a polymerization catalyst in a catalystcomposition for polymerizing conjugated diene polymers, reduces thelevel of aluminum residues at the time of polymerization. However, fromthe standpoint of the rebound and other properties of golf balls,further improvements are desired.

Other prior art relating to the present invention is disclosed in, forexample, JP-A 2002-239034, JP-A 2003-154033, JP-A 2003-190333, JP-A2003-225327, JP-A 2005-089551, JP-A 2005-111049, JP-A 2007-222196, JP-A2008-161345, U.S. Pat. No. 6,277,920, and U.S. Pat. No. 7,244,194.

In view of the foregoing, it is an object of the present invention toprovide a golf ball composition from which golf balls having a goodrebound and an excellent flight performance can be obtained. A furtherobject is to provide a golf ball formed using such a composition.

SUMMARY OF THE INVENTION

As a result of extensive investigations on the types of catalyst andco-catalyst used when polymerizing a diene polymer, the solvent used andthe polymerization temperature, we have discovered high-activitypolymerization conditions under which a large amount of polymer can beobtained in a short period of time with a small amount of catalyst. Thishas made it possible to lower the content of aluminum catalyst residueswhen a diene polymer is polymerized, and has led to the discovery thatcompositions containing such a diene polymer are advantageous forenhancing the golf ball rebound.

Accordingly, the invention provides a golf ball composition whichincludes a diene polymer having an aluminum catalyst residue content ofnot more than 650 ppm.

The diene polymer may have a cis-1,4 bond content of at least 90% and a1,2-vinyl bond content of not more than 2.0%.

The invention also provides a golf ball having a solid core of one ormore layer and, outside of the core, a cover of one or more layer,wherein the solid core is formed of the foregoing golf ball composition.

The golf ball composition of the invention enables golf balls having anespecially good rebound and an excellent flight performance to beobtained.

DETAILED DESCRIPTION OF THE INVENTION

The objects, features and advantages of the invention will become moreapparent from the following detailed description.

The golf ball composition of the invention includes (A) a diene polymerhaving an aluminum catalyst residue content of not more than 650 ppm.

Illustrative examples of the diene polymer serving as component Ainclude polymers which contain units from a conjugated diene compoundsuch as 1,3-butadiene, isoprene, 1,3-pentadiene,2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3,butadiene and 1,3-hexadiene. Inthe practice of the invention, of the above, polymers containing unitsfrom 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene areespecially preferred. The conjugated diene compound may be used singlyor two or more conjugated diene compounds may be used in combination.Examples of aromatic vinyl compounds which may be copolymerized withsuch conjugated diene compounds include styrene, α-methylstyrene,1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene,4-cyclohexylstyrene and 2,4,6-trimethylstyrene. These may be used singlyor two or more may be used in combination.

The weight-average molecular weight (Mw) of component A, although notsubject to any particular limitation, may be set to typically at least20×10⁴, and preferably at least 25×10⁴. The upper limit in theweight-average molecular weight (Mw) of component A is typically notmore than 150×10⁴, and preferably not more than 120×10⁴. If theweight-average molecular weight of component A is too low, a sufficientrebound may not be obtained. On the other hand, if the weight-averagemolecular weight is too high, the workability of the composition maydecline considerably.

Component A has a molecular weight distribution, defined as the ratioMw/Mn of the weight-average molecular weight (Mw) to the number-averagemolecular weight (Mn), which, although not subject to any particularlimitation, may be set to not more than 3, preferably not more than 2.5,more preferably not more than 2, even more preferably not more than 1.9,and most preferably not more than 1.85. The molecular weightdistribution (Mw/Mn), although not subject to any particular lowerlimit, is typically at least 1.0. If the molecular weight distributionof component A is too broad, a sufficient rebound may not be obtainable.One conceivable cause is that the crosslink density is not uniform undersuch circumstances.

In the invention, the weight-average molecular weight (Mw) and thenumber-average molecular weight (Mn) refer to polystyrene-equivalentmolecular weights measured using gel permeation chromatography (GPC).

The cis-1,4 bond content in the diene polymer serving as component A,although not subject to any particular limitation, is typically at least90%, preferably at least 93%, and more preferably at least 95%. Thetrans-1,4 bond content in component A, although not subject to anyparticular limitation, is typically not more than 7%, preferably notmore than 5%, even more preferably not more than 4%, and still morepreferably not more than 3.5%. At a cis-1,4 bond content or a trans-1,4bond content outside of the above ranges, the ball rebound may decrease.

The 1,2-vinyl bond content in component A, although not subject to anyparticular limitation, is typically not more than 3%, preferably notmore than 2.0%, and even more preferably not more than 1.5%. At a1,2-vinyl bond content outside of this range, the ball rebound maydecrease.

Here, in order to lower the amount of aluminum catalyst residue at thetime of polymerization, it is preferable for the diene polymer to besynthesized using as the catalyst at least one type of complex selectedfrom the group consisting of metallocene complexes of general formulas(I) and (II) below, and half-metallocene cation complexes of generalformula (III) below. Moreover, it is desirable for such synthesis to becarried out using a catalyst composition containing also otheringredients, such as a co-catalyst, which are commonly included inmetallocene complex-containing polymerization catalyst compositions.

In formula (I), M is a lanthanide element, scandium or yttrium; eachoccurrence of Cp^(R) is a substituted or unsubstituted indenyl; R^(a) toR^(f) are each independently an alkyl group of 1 to 3 carbons or ahydrogen atom; L is a neutral Lewis base; and w is an integer from 0 to3.

In formula (II), M is a lanthanide element, scandium or yttrium; eachoccurrence of Cp^(R) is a substituted or unsubstituted indenyl; X′ is ahydrogen atom, a halogen atom, an alkoxide group, a thiolate group, anamide group, a silyl group or a hydrocarbon group of 1 to 20 carbons; Lis a neutral Lewis base; and w is an integer from 0 to 3.

In formula (III), M is a lanthanide element, scandium or yttrium;Cp^(R′) is a substituted or unsubstituted cyclopentadienyl, indenyl orfluorenyl; X is a hydrogen atom, a halogen atom, an alkoxide group, athiolate group, an amide group, a silyl group or a hydrocarbon group of1 to 20 carbons; L is a neutral Lewis base; w is an integer from 0 to 3;and [B] is a non-coordinating anion.

In the metallocene complexes of above general formulas (I) and (II),Cp^(R) is a substituted indenyl or an unsubstituted indenyl. Cp^(R)moieties in which an indenyl ring serves as the basic skeleton may berepresented as C₉H_(7-x)R_(x) or C₉H_(11-x)R_(x). Here, x is an integerfrom 0 to 7 or an integer from 0 to 11. Also, it is preferable for eachoccurrence of R to be independently a hydrocarbyl group or a metalloidgroup. The number of carbons on the hydrocarbyl group is preferably from1 to 20, more preferably from 1 to 10, and even more preferably from 1to 8. Preferred examples of the hydrocarbyl group include methyl, ethyl,phenyl and benzyl. The metalloid group (and the metalloid elementtherein) is exemplified by germyl (containing germanium), stannyl(containing tin) and silyl (containing silicon). It is preferable forthe metalloid group to have thereon a hydrocarbyl group, in which casethe hydrocarbyl group on the metalloid group is similar to theabove-described hydrocarbyl group. An illustrative example of themetalloid group is trimethylsilyl. Illustrative examples of substitutedindenyls include 2-phenylindenyl and 2-methylindenyl. The two Cp^(R)moieties in general formulas (I) and (II) may be the same or different.

In the half metallocene cation complex of general formula (III) above,Cp^(R′) in the formula is a substituted or unsubstitutedcyclopentadienyl, indenyl or fluorenyl. Of these, a substituted orunsubstituted indenyl is preferred. Cp^(R′) moieties in which acyclopentadienyl ring serves as the basic skeleton are represented asC₅H_(5-x)R_(x). Here, x is an integer from 0 to 5. It is preferable foreach occurrence of R to be independently a hydrocarbyl group or ametalloid group. The number of carbons on the hydrocarbyl group ispreferably from 1 to 20, more preferably from 1 to 10, and even morepreferably from 1 to 8. Illustrative examples of the hydrocarbyl groupinclude methyl, ethyl, phenyl and benzyl. The metalloid group (and themetalloid element therein) is exemplified by germyl (containinggermanium), stannyl (containing tin) and silyl (containing silicon). Itis preferable for the metalloid group to have thereon a hydrocarbylgroup, in which case the hydrocarbyl group on the metalloid group issimilar to the above-described hydrocarbyl group. An illustrativeexample of the metalloid group is trimethylsilyl. Illustrative examplesof the Cp^(R′) moiety in which a cyclopentadienyl ring serves as thebasic skeleton are shown below.

In the above formula, R is a hydrogen atom, methyl or ethyl.

In general formula (III), the Cp^(R′) moiety in which an indenyl ringserves as the basic skeleton is defined in the same way as Cp^(R) ingeneral formula (I), and preferred examples thereof are also the same.

In general formula (III), the Cp^(R′) moiety in which a fluorenyl ringserves as the basic skeleton may be represented as C₁₃H_(9-x)R_(x) orC₁₃H_(17-x)R_(x). Here, x is an integer from 0 to 9 or an integer from 0to 17. Each occurrence of R is independently a hydrocarbyl group or ametalloid group. The number of carbons on the hydrocarbyl group ispreferably from 1 to 20, more preferably from 1 to 10, and even morepreferably from 1 to 8. Preferred examples of the hydrocarbyl groupinclude methyl, ethyl, phenyl and benzyl. The metalloid group (and themetalloid element therein) is exemplified by germyl (containinggermanium), stannyl (containing tin) and silyl (containing silicon). Itis preferable for the metalloid group to have thereon a hydrocarbylgroup, in which case the hydrocarbyl group on the metalloid group issimilar to the above-described hydrocarbyl group. An illustrativeexample of the metalloid group is trimethylsilyl.

The center metal M in general formulas (I), (II) and (III) is alanthanide element, scandium or yttrium. Lanthanide elements include the15 elements having atomic numbers from 57 to 71, and may be any ofthese. Preferred examples of the center metal M include samarium Sm,neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho,scandium Sc and yttrium Y. In the practice of the invention, from thestandpoint of being able to lower the amount of aluminum catalystresidues during polymerization and thereby conferring the golf ball witha good rebound, neodymium, samarium and gadolinium are more preferred.Gadolinium is especially recommended.

The metallocene complex of general formula (I) includes a silylamideligand [—N(SiR₃)₂]. Each R group included on the silylamide ligand(R^(a) to R^(f) in general formula (I)) may be independently an alkylgroup of 1 to 3 carbons or a hydrogen atom. It is preferable for atleast one of R^(a) to R^(f) to be a hydrogen atom. By having at leastone of R^(a) to R^(f) be a hydrogen atom, catalyst synthesis is easy andbulkiness around the silicon atom decreases, as a result of which anunconjugated olefin is more easily introduced. From a similarstandpoint, it is preferable for at least one of R^(a) to R^(c) to be ahydrogen atom, and for at least one of R^(d) to R^(f) to be a hydrogenatom. The alkyl group is preferably methyl.

The metallocene complex of general formula (II) includes a silyl ligand[—SiX′₃]. The X′ groups included on the silyl ligand [—SiX′₃] are groupsdefined in the same way as X in general formula (III) described below,and the preferred groups are also similar.

In general formula (III), X is a group selected from among hydrogen,halogen atoms, alkoxide groups, thiolate groups, amide groups, silylgroups, and hydrocarbon groups of 1 to 20 carbons. Here, examples ofalkoxide groups include aliphatic alkoxy groups such as methoxy, ethoxy,propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy; and aryloxygroups such as phenoxy, 2,6-di-tert-butylphenoxy,2,6-diisopropylphenoxy, 2,6-dineopentylphenoxy,2-tert-butyl-6-isopropylphenoxy, 2-tert-butyl-6-neopentylphenoxy and2-isopropyl-6-neopentylphenoxy. Of these, a 2,6-di-tert-butylphenoxygroup is preferred.

Thiolate groups represented by X in general formula (III) areexemplified by aliphatic thiolate groups such as thiomethoxy,thioethoxy, thiopropoxy, thio-n-butoxy, thioisobutoxy, thio-sec-butoxyand thio-tert-butoxy; and aryl thiolate groups such as thiophenoxy,2,6-di-tert-butylthiophenoxy, 2,6-diisopropylthiophenoxy,2,6-dineopentylthiophenoxy, 2-tert-butyl-6-isopropylthiophenoxy,2-tert-butyl-6-thioneopentylphenoxy, 2-isopropyl-6-thioneopentylphenoxyand 2,4,6-triisopropylthiophenoxy. Of these, a2,4,6-triisopropylthiophenoxy group is preferred.

Amide groups represented by X in general formula (III) are exemplifiedby aliphatic amide groups such as dimethylamido, diethylamido anddiisopropylamido; aryl amide groups such as phenylamido,2,6-di-tert-butylphenylamido, 2,6-diisopropylphenylamido,2,6-dineopentylphenylamido, 2-tert-butyl-6-isopropylphenylamido,2-tert-butyl-6-neopentylphenylamido, 2-isopropyl-6-neopentylphenylamidoand 2,4,6-tert-butylphenylamido; and bistrialkylsilylamide groups suchas bistrimethylsilylamido. Of these, a bistrimethylsilylamido group ispreferred.

Silyl groups represented by X in general formula (III) are exemplifiedby trimethylsilyl, tris(trimethylsilyl)silyl,bis(trimethylsilyl)methylsilyl, trimethylsilyl(dimethyl)silyl andtriisopropylsilyl(bistrimethylsilyl)silyl. Of these,tris(trimethylsilyl)silyl is preferred.

Halogen atoms represented by X in general formula (III) may be any fromamong fluorine, chlorine, bromine and iodine atoms. Of these, chlorineatoms and bromine atoms are preferred. Illustrative examples ofhydrocarbon groups of 1 to 20 carbons represented by X include linear orbranched aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl,isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, hexyland octyl; aromatic hydrocarbon groups such as phenyl, tolyl andnaphthyl; aralkyl groups such as benzyl; and silicon atom-containinghydrocarbon groups such as trimethylsilylmethyl andbistrimethylsilylmethyl. Of these, methyl, ethyl, isobutyl andtrimethylsilylmethyl are preferred.

In general formula (III), X is preferably a bistrimethylsilylamide groupor a hydrocarbon group of 1 to 20 carbons.

The non-coordinating anion indicated as [B]⁻ in general formula (III) isexemplified by a tetravalent boron anion. Illustrative examples oftetravalent boron anions include tetraphenylborate,tetrakis(monofluorophenyl)borate, tetrakis(difluorophenyl)borate,tetrakis(trifluorophenyl)borate, tetrakis(tetrafluorophenyl)borate,tetrakis(pentafluorophenyl)borate,tetrakis(tetrafluoromethylphenyl)borate, tetra(tolyl)borate,tetra(xylyl)borate, (triphenyl, pentafluorophenyl)borate,[tris(pentafluorophenyl), phenyl]borate andtridecahydride-7,8-dicarbaundecaborate. Of these,tetrakis(pentafluorophenyl)borate is preferred.

The metallocene complexes represented by above general formulas (I) and(II) and the half-metallocene cation complex represented by abovegeneral formula (III) also include from 0 to 3, and preferably 0 or 1,neutral Lewis bases L. Here, the neutral Lewis bases L are exemplifiedby tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine,lithium chloride, neutral olefins and neutral diolefins. In cases wherethe complex includes a plurality of neutral Lewis bases L, the neutralLewis bases L may be the same or different.

The metallocene complexes of general formulas (I) and (II) and thehalf-metallocene cation complex of general formula (III) may exist as amonomer or may instead exist as a dimer or higher multimer.

The metallocene complex of general formula (I) may be obtained by, forexample, reacting a lanthanide trihalide, scandium trihalide or yttriumtrihalide with an indenyl salt (such as a potassium salt or lithiumsalt) and a bis(trialkylsilyl)amide salt (such as a potassium salt orlithium salt) within a solvent. The reaction temperature may be set toabout room temperature, enabling synthesis to be carried out under mildconditions. Moreover, the reaction time may be set to any suitableperiod, such as in a range of from several hours to several tens ofhours. The reaction solvent is not subject to any particular limitation,although a solvent which dissolves the starting materials and theproduct is preferred. For example, toluene may be used. An example of areaction for obtaining the metallocene complex of general formula (I) isshown below.

In the formula, X″ is a halide.

The metallocene complex of general formula (II) may be obtained by, forexample, reacting a lanthanide trihalide, scandium trihalide or yttriumtrihalide with an indenyl salt (such as a potassium salt or lithiumsalt) and a silyl salt (such as a potassium salt or lithium salt) withina solvent. The reaction temperature may be set to about roomtemperature, enabling synthesis to be carried out under mild conditions.Moreover, the reaction time may be set to any suitable period, such asin a range of from several hours to several tens of hours. The reactionsolvent is not subject to any particular limitation, although a solventwhich dissolves the starting materials and the product is preferred. Forexample, toluene may be used. An example of a reaction for obtaining themetallocene complex of general formula (II) is shown below.

In the formula, X″ is a halide.

The half-metallocene cation complex of general formula (III) may beobtained by the following reaction.

Here, in the compound represented by general formula (IV), M is alanthanide element, scandium or yttrium; each occurrence of Cp^(R′) isindependently a substituted or unsubstituted cylopentadienyl, indenyl orfluorenyl; X is a hydrogen atom, a halogen atom, an alkoxide group, athiolate group, an amide group, a silyl group or a hydrocarbon group of1 to 20 carbons; L is a neutral Lewis base; and w is an integer from 0to 3. In the ionic compound represented by general formula [A]⁺[B]⁻,[A]⁺ is a cation and [B]⁻ is a non-coordinating anion.

The cation represented by [A]⁺ is exemplified by carbonium cations,oxonium cations, amine cations, phosphonium cations, cycloheptatrienylcations, and transition metal-bearing ferrocenium cations. Examples ofcarbonium cations include trisubstituted carbonium cations such as thetriphenylcarbonium cation and tri(substituted phenyl)carbonium cations.An example of a tri(substituted phenyl)carbonyl cation is thetri(methylphenyl)carbonium cation. Examples of amine cations includetrialkylammonium cations such as the trimethylammonium cation,triethylammonium cation, tripropylammonium cation and tributylammoniumcation; N,N-dialkylanilinium cations such as the N,N-dimethylaniliniumcation, N,N-diethylanilinium cation and N,N-2,4,6-pentamethylaniliniumcation; and dialkylammonium cations such as the diisopropylammoniumcation and dicyclohexylammonium cation. Examples of phosphonium cationsinclude the triphenylphosphonium cation, tri(methylphenyl)phosphoniumcation and tri(dimethylphenyl)phosphonium cation. Of these cations, anN,N-dialkylanilinium cation or a carbonium cation is preferred. AnN,N-dialkylanilinium cation is especially preferred.

The ionic compound of general formula [A]⁺[B]⁻ used in the abovereaction is a compound in which one of the above non-coordinating anionshas been combined with one of the above cations. Preferred examplesinclude N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate andtriphenylcarbonium tetrakis(pentafluorophenyl)borate. The ionic compoundof the general formula [A]⁺[B]⁻ is added in an amount of preferably fromabout 0.1 to about 10 moles, and more preferably about 1 mole, per moleof the metallocene complex. When a half-metallocene cation complex ofgeneral formula (III) is used in the polymerization reaction, thehalf-metallocene cation complex of general formula (III) may befurnished directly in this form to the polymerization reaction system,or the compound of general formula (IV) and the ionic compound ofgeneral formula [A]⁺[B]⁻ used in the reaction may be furnishedseparately to the polymerization reaction system and thehalf-metallocene cation complex of general formula (III) may be formedwithin the reaction system. Alternatively, a half-metallocene cationcomplex of general formula (III) may be formed within the reactionsystem by using a metallocene complex of general formula (I) or (II) incombination with an ionic compound of general formula [A]⁺[B]⁻.

The structures of the metallocene complexes of general formulas (I) and(II) and of the half-metallocene cation complex of general formula (III)are preferably determined by x-ray structural analysis.

Co-catalysts which may be used in the polymerization catalystcomposition may be freely selected from among ingredients which are usedas co-catalysts in conventional metallocene complex-containingpolymerization catalyst compositions. Preferred co-catalysts includealuminoxanes, organoaluminum compounds, and the above-mentioned ioniccompounds. These co-catalysts may be used singly, or two or more may beused in combination.

The aluminoxane is preferably an alkyl aluminoxane, such as methylaluminoxane (MAO) or a modified methyl aluminoxane. An example of amodified methyl aluminoxane is MAO-3A (available from Tosoh FinechemCorporation). The aluminoxane content in the polymerization catalystcomposition, expressed as the elemental ratio Al/M of the center metal Min the metallocene complex to the aluminum element Al in thealuminoxane, is set to preferably from about 10 to about 1,000, and morepreferably about 100.

The above organoaluminum compound is preferably an organoaluminumcompound of the general formula AlRR′R″ (wherein R and R′ are eachindependently a C₁₋₁₀ hydrocarbon group or a hydrogen atom, and R″ is aC₁₋₁₀ hydrocarbon group). Exemplary organoaluminum compounds includetrialkylaluminums, dialkylaluminums, dialkylaluminum chlorides,alkylaluminum dichlorides and dialkylaluminum hydrides. Of these,trialkylaluminums and dialkylaluminums are preferred. Preferred examplesinclude triethylaluminum, triisobutylaluminum and diisobutylaluminum.The content of the organoaluminum compound in the polymerizationcatalyst composition is preferably from 1 to 500 moles per mole of themetallocene complex.

The reaction conditions when carrying out polymerization using the abovecatalyst composition may be suitably selected according to the type ofmonomer or the type of catalyst composition, and is not subject to anyparticular limitation. For example, the polymerization temperature maybe set in a range of generally from −100 to +100° C., and preferablyfrom −50 to +80° C. The polymerization time may be set to generally fromabout 1 minute to about 12 hours, and preferably from about 5 minutes toabout 5 hours. When the polymerization reaction proceeds and theintended degree of polymerization has been attained, the reaction isstopped by adding a known shortstopper to the polymerization system,after which a conventional technique may be used to separate the polymerthat has formed from the reaction system.

It is critical for the content of aluminum catalyst residues in thediene polymer which has been polymerized to be not more than 650 ppm,preferably not more than 550 ppm, and more preferably not more than 300ppm. At too high an aluminum catalyst residue content, the rebound willdecrease. The reason why lowering the content of aluminum catalystresidues in the diene polymer improves the rebound is thought to be thatthe crosslink density of the polymer increases, reducing energy loss.

The diene polymer serving as component A may be a diene polymer whereina plurality of molecular chains have been coupled together or the endshave been modified using a coupling agent or a polyvalent modifier,either during polymerization or after polymerization. The couplingagent/polyvalent modifier is exemplified by tin, silicon, phosphorus ornitrogen-containing compounds, epoxy group-containing compound, estercompounds and carboxylic acids. Illustrative examples include tintetrachloride, silicon tetrachloride, phosphorus trichloride, dibutyltindichloride, dioctyltin bisoctylmaleate (DOTBOM), polyisocyanatecompounds, polymethyl methacrylate, maleic acid, and3-glycidyloxypropyltrimethoxysilane. The coupling reaction atpolymerization active sites by the coupling agent/polyvalent modifier ispreferably carried out by a solution reaction. It doesn't matter whetherthe monomer used at the time of polymerization may be left in thesolution or not. The application of the coupling reaction is notparticularly limited, could be employed in either a batch-typepolymerization or a continuous polymerization. In addition, the reactiontemperature in the coupling reaction is not subject to any particularlimitation, so long as the reaction proceeds. Thus, for example, thereaction temperature in the polymerization reaction may also be usedwithout modification in the coupling reaction. The amount of couplingagent/polyvalent modifier used is not subject to any particularlimitation, provided some or all of the plurality of molecular chains onthe polymer having active ends are converted to dimers, trimers orhigher multimers. By using such coupling agents and polyvalent modifiersand reacting them with the diene polymer, a plurality of molecularchains are coupled linearly or as branched stars, thereby improving thecold flow properties of the diene polymer itself, and in turn givingrise to, for example, an increased golf ball rebound.

Alternatively, the diene polymer serving as component A may be a dienepolymer synthesized by reacting a monovalent modifier or the like andhaving functional groups at the ends of the molecule or on the molecularchain. These functional groups confer the golf ball composition withimproved cold flow properties due to interactions between the functionalgroups, and also impart, for example, an increased golf ball rebound anddurability and an increased processability due to reactions and otherinteractions with fillers and other ingredients included in the golfball composition.

Other rubber ingredients may also be included in the golf ballcomposition of the invention, insofar as the objects of the inventionare achievable. Examples of such other rubber ingredients includepolybutadiene obtained using a group VIII metal compound catalyst, andalso styrene-butadiene rubber, natural rubber, isoprene rubber andethylene-propylene-diene rubber.

In addition, the golf ball composition of the invention may alsooptionally include various additives such as (B) an unsaturatedcarboxylic acid, (C) an inorganic filler, (D) an organic peroxide, (E)an antioxidant, and (F) an organosulfur compound. These additives aredescribed in detail below.

Illustrative examples of the unsaturated carboxylic acid (B) includeacrylic acid, methacrylic acid, maleic acid and fumaric acid. Acrylicacid and methacrylic acid are especially preferred. Metal salts of theunsaturated carboxylic acid include zinc salts and magnesium salts. Ofthese, preferred use may be made of zinc acrylate.

The amount of component B included, although not subject to anyparticular limitation, may be set to typically at least 10 parts byweight, preferably at least 13 parts by weight, more preferably at least16 parts by weight, even more preferably at least 18 parts by weight,and most preferably at least 20 parts by weight, per 100 parts by weightof component A. The upper limit in the amount of component B may be setto typically not more than 60 parts by weight, preferably not more than50 parts by weight, more preferably not more than 45 parts by weight,even more preferably not more than 40 parts by weight, and mostpreferably not more than 35 parts by weight. If too little component Bis included, a sufficient hardness may not achieved. On the other hand,if too much is included, the composition may become too hard, possiblyresulting in a poor durability to use.

Illustrative examples of the inorganic filler (C) include zinc oxide,barium sulfate and calcium carbonate. The amount of inorganic fillerincluded, although not subject to any particular limitation may be setto at least 1 part by weight, preferably at least 5 parts by weight,more preferably at least 9 parts by weight, and even more preferably atleast 13 parts by weight, per 100 parts by weight of component A. Theupper limit in the amount of component C may be set to typically notmore than 80 parts by weight, preferably not more than 65 parts byweight, more preferably not more than 50 parts by eight, and even morepreferably not more than 40 parts by weight. At an amount of component Coutside the above range, it may not be possible to obtain a proper ballweight and a suitable rebound.

Illustrative examples of the organic peroxide (D) include dicumylperoxide, 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane and1,1-di(t-butylperoxy)cyclohexane. Commercial products may be used asthese organic peroxides. Illustrative examples include Percumyl D,Perhexa 3M and Perhexa C-40 (all available from NOF Corporation).

The organic peroxide may be used singly or may be used as a combinationof two or more types. From the standpoint of rebound in particular, thecombined use of two or more organic peroxides is preferred. Although notsubject to any particular limitation, letting the organic peroxidehaving the shortest half-life at 155° C. be component D−1 and theorganic peroxide having the longest half-life be component D−2, andletting the half-life of component D−1 be (D−1)_(t) and the half-life ofcomponent D−2 be (D−2)_(t), it is desirable to combine two organicperoxides such that the half-life ratio (D−2)_(t)/(D−1)_(t) ispreferably at least 7, more preferably at least 8, even more preferablyat least 9, and most preferably at least 10. Although not subject to anyparticular limit, the half-life ratio may be set to preferably not morethan 20, more preferably not more than 18, even more preferably not morethan 16, and most preferably not more than 14. At a half-life ratiooutside of the above range, even when two or more organic peroxides areused, golf ball properties such as rebound, compression and durabilitymay worsen.

Here, although not subject to any particular limitation, the half-life(D−1)_(t) of component D−1 at 155° C. is typically at least 5 seconds,preferably at least 10 seconds, and more preferably at least 15 seconds.The upper limit is typically not more than 120 seconds, preferably notmore than 90 seconds, and more preferably not more than 60 seconds. Thehalf-life (D−2)_(t) of component D−2 at 155° C., which also is notsubject to any particular limitation, is typically at least 300 seconds,preferably at least 360 seconds, and more preferably at least 420seconds. The upper limit is typically not more than 800 seconds,preferably not more than 700 seconds, and even more preferably not morethan 600 seconds. In the practice of the invention, the organic peroxideserving as component D−1 is preferably1,1-bis(t-butylperoxy)cyclohexane, and the organic peroxide serving ascomponent D−2 is preferably dicumyl peroxide.

The combined amount of the above organic peroxides included, althoughnot subject to any particular limitation, is typically at least 0.05part by weight, preferably at least 0.1 part by weight, and morepreferably at least 0.15 part by weight, per 100 parts by weight ofcomponent A. Although not subject to any particular upper limit, thecombined amount of the organic peroxides is typically not more than 3parts by weight, preferably not more than 2 parts by weight, morepreferably not more than 1 part by weight, even more preferably not morethan 0.8 part by weight, and most preferably not more than 0.6 part byweight, per 100 parts by weight of component A. If too little isincluded, the time required for crosslinking will increase, as a resultof which the productivity may decrease markedly and the compression mayalso undergo a large decline. On the other hand, if too much isincluded, the rebound and durability may decrease.

When above components D−1 and D−2 are used in combination as the organicperoxide, the amount of component D−1 added, although not subject to anyparticular limitation, is typically at least 0.05 part by weight,preferably at least 0.08 part by weight, and more preferably at least0.1 part by weight, per 100 parts by weight of component A. The upperlimit is typically not more than 0.5 part by weight, preferably not morethan 0.4 part by weight, and more preferably not more than 0.3 part byweight. The amount of component D−2 added, although likewise not subjectto any particular limitation, is typically at least 0.05 part by weight,preferably at least 0.15 part by weight, and more preferably at least0.2 part by weight, per 100 parts by weight of component A. The upperlimit is typically not more than 0.7 part by weight, preferably not morethan 0.6 part by weight, and more preferably not more than 0.5 part byweight.

The above composition may also include an antioxidant (E). A commercialproduct may be used as this antioxidant. For example, preferred use maybe made of Nocrac NS-6, Nocrac NS-30 (both available from Ouchi ShinkoChemical Industry Co., Ltd.), and Yoshinox 425 (Yoshitomi PharmaceuticalIndustries, Ltd.). The amount of component E included, although notsubject to any particular limitation, may be set to typically at least0.05 part by weight per 100 parts by weight of component A. The upperlimit may be set to typically not more than 3 parts by weight,preferably not more than 2 parts by weight, more preferably not morethan 1 part by weight, and even more preferably not more than 0.5 partby weight.

Exemplary organosulfur compounds (F) include thiophenols, thionaphthols,halogenated thiophenols, and metal salts thereof. Illustrative examplesinclude pentachlorothiophenol, pentafluorothiophenol,pentabromothiophenol, p-chlorothiophenol, and zinc salts thereof;diphenylpolysulfides, dibenzylpolysulfides, dibenzoylpolysulfides,dibenzothiazoylpolysulfides and dithiobenzoylpolysulfides having 2 to 4sulfurs; alkylphenyldisulfides; and furan ring-bearing sulfur compoundsand thiophene ring-bearing sulfur compounds. In the practice of theinvention, the use of diphenyldisulfide or the zinc salt ofpentachlorothiophenol is especially preferred.

The amount of component F included, although not subject to anyparticular limitation, is typically at least 0.05 part by weight,preferably at least 0.2 part by weight, more preferably at least 0.4part by weight, even more preferably at least 0.7 part by weight, andmost preferably at least 0.9 part by weight, per 100 parts by weight ofcomponent A. The upper limit in the amount included is typically notmore than 5 parts by weight, preferably not more than 4 parts by weight,more preferably not more than 3 parts by weight, even more preferablynot more than 2 parts by weight, and most preferably not more than 1.5parts by weight, per 100 parts by weight of component A. If too littlecomponent F is included, a sufficient rebound may not be achieved. Onthe other hand, including too much may excessively lower the hardness,which may also prevent a sufficient rebound from being achieved.

The golf ball of the invention may take any of various forms accordingto the intended purpose thereof without particular limitation, providedthe above-described golf ball composition is used in at least someportion of an integral part of the ball. Illustrative examples includeone-piece golf balls formed entirely of the above composition; two-piecesolid golf balls having a solid core and one cover layer, wherein atleast some portion of the solid core and/or the cover is formed of theabove composition; multi-piece solid golf balls composed of three ormore pieces, which balls have a solid core of one or more layer and acover of one or more layer, wherein at least some portion of the solidcore and/or the cover is formed of the above composition; and wound golfballs wherein at least some portion of the solid center and/or the coveris formed of the above composition. Of these various forms, particularlyin order to take full advantage of the properties of the composition andmore effectively achieve a good golf ball rebound, a two-piece solidgolf ball or multi-piece solid golf ball having a solid core formed ofthe above composition is preferred.

Examples of materials which may be used in portions of the golf ballother than the portion where the inventive golf ball composition is usedinclude thermoplastic or thermoset polyurethane elastomers, polyesterelastomers, ionomer resins, polyolefin elastomers and polyureas. Onesuch material may be used alone or two or more may be used in admixture.The use of a thermoplastic polyurethane elastomer or an ionomer resin isespecially preferred. The molding process employed may be a knownprocess such as injection molding or compression molding.

A commercial product may be used as the thermoplastic polyurethaneelastomer. Illustrative examples include Pandex T7298, Pandex T7295,Pandex T7890, Pandex TR3080, Pandex T8295, Pandex T8290 and Pandex T8260(available from DIC Bayer Polymer, Ltd.). A commercial product may beused as the ionomer resin as well. Illustrative examples include Surlyn6320, Surlyn 8120 and Surlyn 9945 (available from E.I. DuPont de Nemours& Co.), and Himilan 1706, Himilan 1605, Himilan 1855, Himilan 1601 andHimilan 1557 (available from DuPont-Mitsui Polychemicals Co., Ltd.).

Polymers such as thermoplastic elastomers other than those mentionedabove may be included as optional ingredients in the above material.Examples of such other polymers include polyamide elastomers, styreneblock elastomers, hydrogenated polybutadienes and ethylene-vinyl acetate(EVA) copolymers.

In cases where the golf ball of the invention is a one-piece golf ballor a golf ball having a solid core or a solid center, the deflection ofthe one-piece golf ball or the solid core or solid center, whencompressed under a final load of 1,275 N (130 kgf) from an initial loadstate of 98 N (10 kgf), although not subject to any particularlimitation, is typically at least 2.0 mm, and preferably at least 2.5mm. The upper limit is typically not more than 6.0 mm, and preferablynot more than 5.8 mm. If the deflection is too small, the feel on impactmay worsen and, particularly on a long shot such as with a driver thatcauses a large deformation of the ball, the spin rate may riseexcessively, resulting in a poor distance. On the other hand, if theone-piece golf ball or the solid core or solid center is too soft, theball may have a deadened feel on impact and the rebound may beinadequate, possibly resulting in a poor distance, or the durability ofthe ball to cracking on repeated impact may worsen.

The diameter of the solid core, although not subject to any particularlimitation, may be set to generally at least 20 mm, and preferably atleast 30 mm. The upper limit may be set to generally not more than 42.5mm, and preferably not more than 42.3 mm.

The specific gravity of the solid core, although not subject to anyparticular limitation, may be set to generally at least 0.7, andpreferably at least 0.9. The upper limit may be set to generally notmore than 1.6, and preferably not more than 1.4.

The thickness per cover layer formed of the inventive golf ballcomposition and the above-mentioned materials, although not subject toany particular limitation, may be set to generally at least 0.1 mm, andpreferably at least 0.2 mm. The upper limit may be set to generally notmore than 4 mm, and preferably not more than 3 mm.

In cases where the rubber composition of the invention is used toproduce one-piece golf balls, two-piece solid golf balls and multi-piecesolid golf balls, production may be carried out by effectingvulcanization and curing in the same way as with conventional rubbercompositions for golf balls. The vulcanization conditions areexemplified by a vulcanization temperature of from 100 to 200° C. and avulcanization time of from 10 to 40 minutes.

The diameter of the inventive golf ball may be set to not less than 42mm, and in particular, according to the Rules of Golf for competitiveplay, preferably not less than 42.67 mm. The upper limit may be set tonot more than 45 mm, and preferably not more than 44 mm. The weight maybe set to not more than 48 g, and in particular, according to the Rulesof Golf for competitive play, preferably not more than 45.93 g. Thelower limit may be set to not less than 40 g, and preferably not lessthan 44 g.

EXAMPLES

Examples according to the invention and Comparative Examples are givenbelow by way of illustration, and not by way of limitation.

Example 1

A catalyst solution was prepared by charging a 1-literpressure-resistant glass reactor within a glove box under a nitrogenatmosphere with 15.4 μmol of bis(2-phenylindenyl)gadoliniumbis(dimethylsilylamide) [(2-PhC₉H₆)₂GdN(SiHMe₂)₂], 15.4 μmol oftriphenylcarbonium tetrakis(pentafluorophenyl)borate (Ph₃CB(C₆F₅)₄) and1.5 mmol of diisobutylaluminum, then dissolving these ingredients in 5.0g of toluene and carrying out 30 minutes of aging. The reactor wassubsequently removed from the glove box, 467 g of a toluene solutioncontaining 15 wt % of 1,3-butadiene was added, and polymerization wascarried out at 50° C. for 1 hour. Following polymerization, the reactionwas stopped by adding 1 mL of an isopropanol solution containing 5 wt %of 2,2′-methylenebis(4-ethyl-6-t-butylphenol) (available from OuchiShinko Chemical Industry Co., Ltd. under the trade name “Nocrac NS-5”).The polymer was separated off using a large amount of methanol, thenvacuum-dried at 70° C., thereby giving diene polymer A. The yield of theresulting diene polymer A was 65.9 g.

Example 2

A catalyst solution was prepared by charging a 1-literpressure-resistant glass reactor within a glove box under a nitrogenatmosphere with 4.9 μmol of bis(2-phenylindenyl)gadoliniumbis(dimethylsilylamide) [(2-PhC₉H₆)₂GdN(SiHMe₂)₂], 4.9 μmol oftriphenylcarbonium tetrakis(pentafluorophenyl)borate (Ph₃CB(C₆F₅)₄) and1.2 mmol of diisobutylaluminum, then dissolving these ingredients in 5.0g of toluene and carrying out 30 minutes of aging. The reactor wassubsequently removed from the glove box, 533 g of a toluene solutioncontaining 15 wt % of 1,3-butadiene was added, and polymerization wascarried out at 50° C. for 1 hour. Following polymerization, the reactionwas stopped by adding 1 mL of an isopropanol solution containing 5 wt %of 2,2′-methylenebis(4-ethyl-6-t-butylphenol) (available from

Ouchi Shinko Chemical Industry Co., Ltd. under the trade name “NocracNS-5”). The polymer was separated off using a large amount of methanol,then vacuum-dried at 70° C., thereby giving diene polymer B. The yieldof the resulting diene polymer B was 63.0 g.

Example 3

A catalyst solution was prepared by charging a 1-literpressure-resistant glass reactor within a glove box under a nitrogenatmosphere with 4.8 μmol of bis(2-phenylindenyl)gadoliniumbis(dimethylsilylamide) [(2-PhC₉H₆)₂GdN(SiHMe₂)₂], 4.8 μmol oftriphenylcarbonium tetrakis(pentafluorophenyl)borate (Ph₃CB(C₆F₅)₄) and0.5 mmol of diisobutylaluminum, then dissolving these ingredients in 5.0g of toluene and carrying out 30 minutes of aging. The reactor wassubsequently removed from the glove box, 400 g of a toluene solutioncontaining 15 wt % of 1,3-butadiene was added, and polymerization wascarried out at 50° C. for 1 hour. Following polymerization, the reactionwas stopped by adding 1 mL of an isopropanol solution containing 5 wt %of 2,2′-methylenebis(4-ethyl-6-t-butylphenol) (available from OuchiShinko Chemical Industry Co., Ltd. under the trade name “Nocrac NS-5”).The polymer was then separated off with a large amount of methanol, thenvacuum-dried at 70° C., thereby giving diene polymer C. The yield of theresulting diene polymer C was 57.7 g.

Comparative Example 1

The polybutadiene rubber available under the trade name “BR730” from JSRCorporation, was used as a comparative example with respect to abovediene polymers A to C.

The properties of the polymers in Examples 1 to 3 and ComparativeExample 1 are shown in Table 1.

TABLE 1 Comparative Example Example 1 2 3 1 Type diene diene diene BR730polymer polymer polymer A B C Mw (×10⁴) 46.4 39.8 108.5 44.2 Mn (×10⁴)20.5 25.3 59.3 16.1 Mw/Mn 2.30 1.57 1.83 2.31 cis-1,4 Bond content (%)98.7 98.4 97.0 97.0 trans-1,4 Bond content (%) 0.9 1.3 1.7 2.4 1,2-Vinylbond content (%) 0.4 0.4 1.3 0.6 Aluminum catalyst residue 631.2 502.0224.6 1,800 content (ppm) Details on various items in Table 1 are givenbelow. BR730: A polybutadiene produced by JSR Corporation cis-1,4-Bondcontent (%): Proportion of cis-1,4 bonds in the diene polymertrans-1,4-Bond content (%): Proportion of trans-1,4 bonds in the dienepolymer 1,2-Vinyl bond content (%): Proportion of 1,2-vinyl bonds in thediene polymer

The microstructures (cis-1,4 bond contents, trans-1,4 bond contents and1,2-vinyl bond contents), weight-average molecular weights (Mw),molecular weight distributions (Mw/Mn) and aluminum catalyst residuecontents of the polymers in Examples 1 to 3 and Comparative Example 1were measured by the following methods.

(1) Microstructures

The FT-IR transmission spectrum of a carbon disulfide solution of thebutadiene polymer prepared to a concentration of 5 mg/mL was measuredagainst carbon disulfide alone in the same cell as a blank. Using thevalues e, f and g derived from the following determinant

${{\begin{bmatrix}{1{.7455}} & 0 & {- 0.0151} \\{{- 0}{.0454}} & 0.4292 & {- 0.0129} \\{{- 0}{.007}} & 0 & 0.3746\end{bmatrix}\begin{bmatrix}{\log_{10}\left( {a/d} \right)} \\{\log_{10}\left( {a/b} \right)} \\{\log_{10}\left( {a/c} \right)}\end{bmatrix}} = \begin{bmatrix}e \\f \\g\end{bmatrix}},$

wherein a is the positive peak value near 1130 cm⁻¹ in the spectrum, bis the negative peak value near 967 cm⁻¹, c is the negative peak valuenear 911 cm⁻¹ and d is the negative peak value near 736 cm⁻¹, thecis-1,4 bond content, trans-1,4 bond content and 1,2-vinyl bond contentwere determined from the following formulas (i) , (ii) and (iii):

cis-1,4 bond content (%)=e/(e+f+g)×100   (i)

trans-1,4 bond content (%)=f/(e+f+g)×100   (ii)

1,2-vinyl bond content (%)=g/(e+f+g)×100   (iii).

The positive peak value a near 1130 cm⁻¹ in the above spectrum indicatesthe baseline, the negative peak value b near 967 cm⁻¹ indicates thetrans-1,4 bonds, the negative peak value c near 911 cm⁻¹ indicates the1,2-vinyl bonds, and the negative peak value d near 736 cm⁻¹ indicatesthe cis-1,4 bonds. The microstructure contents in Table 1 are valuesrounded off to the nearest tenth.

(2) Weight-Average Molecular Weight (Mw) and Molecular WeightDistribution (Mw/Mn)

Measurement was carried out by gel permeation chromatography (GPC) (withan HLC-8020 system from Tosoh Corp.) and using a refractometer as thedetector. The molecular weight was indicated as the polystyreneequivalent, with monodispersed polystyrene serving as the standard. AGMHXL column (Tosoh Corp.) was used, and the eluant was tetrahydrofuran.

(3) Aluminum Catalyst Residue Content

The content of aluminum catalyst residues was measured by elementalanalysis.

Using the polymers obtained as described above, compositions formulatedas shown in Table 2 were prepared, following which the compositions weremolded and vulcanized at 160° C. for 15 minutes, thereby fabricatingsolid cores having a diameter of 38.5 mm and a weight of 35.6 g. Theinitial velocities (rebounds) of the solid cores thus fabricated wereevaluated by the subsequently described method. The results are shown inTable 2.

TABLE 2 Comparative Example Example 1 2 3 1 Formula- Polymer A 100 tion(pbw) Polymer B 100 Polymer C 100 BR730 100 Zinc oxide 22 22 22 22Antioxidant 0.1 0.1 0.1 0.1 Zinc acrylate 30 30 30 30 Percumyl D 0.3 0.30.3 0.3 Perhexa C-40 0.3 0.3 0.3 0.3 Perfor- Initial velocity +0.19+0.31 +0.45 — mance difference (m/s) evaluation Details on some of theingredients in Table 2 are given below. Zinc oxide: Grade 3 zinc oxide,available from Sakai Chemical Co., Ltd. Antioxidant:2,2′-Methylenebis(4-methyl-6-t-butylphenol), available from Ouchi ShinkoChemical Industry Co., Ltd., under the trade name “Nocrac NS-6” Zincacrylate: Available from Nippon Shokubai Co., Ltd. Percumyl D: Dicumylperoxide, available from NOF Corporation Perhexa C-40: 40% Dilution of1,1-di(t-butylperoxy)-cyclohexane, available from NOF CorporationInitial Velocity of Solid Core (m/s)

The initial velocity of the solid core was measured using an initialvelocity measuring apparatus of the same type as the USGA drumrotation-type initial velocity instrument approved by the R&A. The corewas held isothermally at a temperature of 23±1° C. for at least 3 hours,then tested in a room temperature (23±2° C.) chamber.

Table 2 shows the difference of the measured value obtained in eachexample of the invention relative to a reference value of “0” forComparative Example 1.

Japanese Patent Application No. 2011-269007 is incorporated herein byreference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

1. A golf ball composition comprising a diene polymer, wherein the dienepolymer has an aluminum catalyst residue content of not more than 650ppm.
 2. The composition of claim 1, wherein the diene polymer has acis-1,4 bond content of at least 90% and a 1,2-vinyl bond content of notmore than 2.0%.
 3. A golf ball comprising a solid core of one or morelayer and, outside of the core, a cover of one or more layer, whereinthe solid core is formed of the golf ball composition of claim 1.